Chemistry 500 Dr. Hunter’s Class Topic 2. 1 Chemistry 500: Chemistry in Modern Living Topic 2: Protecting the Ozone Layer Atoms and Light Chemistry in Context, 2nd Edition: Chapter 2, Pages 35-72 Chemistry in Context, 3rd Edition: Chapter 2, Pages 45-92 Outline Notes by Dr. Allen D. Hunter, YSU Department of Chemistry, 2000. 2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University Chemistry 500 Dr. Hunter’s Class Topic 2. 2 Outline 2A WHAT IS OZONE? ...........................................................................................................................................3 2B WHAT IS THE STRUCTURE OF A ATOM?................................................................................................6 2C HOW DO WE KNOW MOLECULAR STRUCTURES? ............................................................................ 11 2D HOW DO WE EXPLAIN MOLECULAR STRUCTURES? ....................................................................... 13 2E WAVES OF LIGHT ........................................................................................................................................ 17 2F WAVE/PARTICLE DUALITY ...................................................................................................................... 20 2G THE OZONE SCREEN ................................................................................................................................... 21 2H CFCS AND OZONE ........................................................................................................................................ 26 2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University Dr. Hunter’s Class Chemistry 500 2A What is Ozone? Ozone Formation Produced from a variety of processes: Photochemical Smog (Topic 1) High Voltage Electrical Discharges Molecular Oxygen + Energy Ozone 3 O2 + Energy 2 O3 Can be smelled at 10 ppb Arc Welding Lightning Storms Laser Printers Tesla Coils 2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University Topic 2. 3 Dr. Hunter’s Class Chemistry 500 Topic 2. 4 Allotropes Different forms of the same element They have different chemical structures Hence different chemical properties Examples include: Graphite (found in pencil lead) and Diamond (on rings) are different chemical forms of the element Carbon Molecular Oxygen and Ozone are different chemical forms of the element Oxygen 2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University Dr. Hunter’s Class Chemistry 500 Topic 2. The Allotropes of the Element Oxygen Molecular Oxygen, O2 A Diatomic Molecule Liquefies at -183 C A light blue liquid Odorless Ozone, O3 A Triatomic Molecule Liquefies at -112 C A dark blue liquid Used in water purification and pulp and paper bleaching Characteristic Odor 2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University 5 Dr. Hunter’s Class Chemistry 500 Topic 2. 6 2B What is the Structure of a Atom? Graphics from Text: Table 2.1, the Properties of Sub-Atomic Particles Overview of Atoms and Nuclei Diagram Not to Scale! Nucleus actually tremendously smaller than the electron cloud The Electron Cloud includes both Core Electrons and Valence Electrons e- P+ N N 2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University Dr. Hunter’s Class Chemistry 500 Topic 2. 7 Electrons, e Surround the Nucleus Mass of 1/1838 AMU Charge of -1 Protons, P+ In the Nucleus Mass of 1 AMU Charge of +1 Neutron, n In the Nucleus Mass of 1 AMU Charge of 0 Neutron/Proton Ratio in Stable Nuclei Due to balance of Strong Nuclear Force and Electrostatic Force 2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University Dr. Hunter’s Class Chemistry 500 Topic 2. 8 Evidence for this structure High Energy Diffraction / Collision Experiments Rubber Baggie model of nucleus Isotopes The same element (i.e., the same number of protons in the nucleus) Different Mass due to different number of Neutrons in the Nucleus Chemically Isotopes react extremely similarly Examples: 1H(Hydrogen), 2H (D, Deuterium), and 3H (T, Tritium) 12C (common, 99%), 13 C (rare, 1%, NMR), and rare, produced in upper atmosphere, radioactive) 238 U (non-radioactive) and 235U (radioactive) 2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University 14 C (very Dr. Hunter’s Class Chemistry 500 Topic 2. 9 The Periodic Table Use the Periodic Table to Evaluate the Number of e-, P+, and n in each isotope Atomic Number The number of Electrons and Protons in the neutral atom Mass Number The total number of Protons and Neutrons He 4 # e- = # P+ = #n = Ar 40 # e- = # P+ = #n = 2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University Dr. Hunter’s Class Chemistry 500 Topic 2. 10 Ask Students: For each of the following isotopes, give the total number of protons, neutrons, and electrons and then the number of valence electrons and core electrons. Group Activity Be 7 # e- = # P+ = #n = C 13 # e- = # P+ = #n = F 19 # e- = # P+ = #n = Si 29 # e- = # P+ = #n = 183 W # e- = # P+ = #n = 2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University Dr. Hunter’s Class Chemistry 500 Topic 2. 11 2C How Do We Know Molecular Structures? How do we know molecular structures? Analytical Data Spectroscopic Methods Sporting Methods Specific absorption of light NMR = Nuclear Magnetic Resonance (cf. MRI, Magnetic Resonance Imaging) Infra-Red (IR) Ultra Violet-Visible (UV-Vis) From the mid 1850s have know many molecular shapes but were not able to explain them other than to say the atoms were connected 2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University Dr. Hunter’s Class Chemistry 500 X-Ray Crystallography/Diffraction Non-Sporting Method Single Crystals Hardware Data Collection Data Analysis 2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University Topic 2. 12 Dr. Hunter’s Class Chemistry 500 Topic 2. 13 2D How Do We Explain Molecular Structures? Theories change over time to better fit the experimental data A Theory should explain all current data and predict future results Lewis Dot Structures Lewis developed this theory to explain know molecular structures, reactivity data, and emerging ideas like electricity and radioactivity Bonds were due to shared pairs of electrons Lone Pairs of Valence Electrons remain on many atoms Only the Valence Electrons Contribute to bonding This accounts for the fact that elements underneath one another on the periodic table react similarly 2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University Dr. Hunter’s Class Chemistry 500 Topic 2. 14 Rigorous Method of Determining Lewis Dot Structures Count the total number of valence electrons for the molecules Distribute them around the atoms such that each atom gets as close to a complete Octet as possible An Octet is 8 for most elements but 2 for Hydrogen and Helium Some elements will allow / settle for greater or lesser than 8 electrons but we won’t see these in Chem. 500 H H H C H C C C H 2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University S H Dr. Hunter’s Class Chemistry 500 Topic 2. 15 Quick and Dirty Method for getting Lewis Structures An oversimplification that can break down but works well for most Organic Compounds Bond Lengths Bond Angles H one bond and no lone pairs F, Cl, Br, and I one bond and three lone pairs O, S, Se, and Te two bonds and two lone pairs N, P, As, and Sb three bonds and one lone pair C, Si, Sn, and Ge four bonds and no lone pairs H H H C H C C C H 2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University S H Dr. Hunter’s Class Chemistry 500 Topic 2. 16 Ask Students: For each of the following molecules, draw the correct Lewis Dot Structures including all Bonds and Lone Pairs Group Activity H H O H H C C C C H H H H H H Cl C C C Cl H H C H O O C H H H H H C C I H Se O N C H H 2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University H Dr. Hunter’s Class Chemistry 500 Topic 2. 17 2E Waves of Light Graphics from Text: Figure 2.1, Wave Motion The relationship between Frequency, Wavelength, and Amplitude for Electromagnetic Waves Electromagnetic Spectrum Wavelength of Electromagnetic Waves Long wavelengths correspond to low energy waves Is inversely related to the Frequency of Electromagnetic Waves Wavelength = Speed of Light / Frequency = C / C = Speed of Light = 3 x 108 m/sec 2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University Dr. Hunter’s Class Chemistry 500 Topic 2. 18 Frequency of Electromagnetic Waves High frequency corresponds to high energy waves Is inversely related to the Wavelength of Electromagnetic Waves Frequency = Speed of Light / Wavelength = C / Amplitude of Electromagnetic Waves Is related to the intensity of the wave 2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University Dr. Hunter’s Class Chemistry 500 Topic 2. 19 Graphics from Text: Figure 2.2, the Electromagnetic Spectrum The relationship between frequency and wavelength for various types of electromagnetic radiation Graphics from Text: Figure 2.3, Solar Radiation Profile The distribution of electromagnetic radiation of various energies produced by the sun as they appear from just above the earth’s atmosphere Note: the Overall Profile (Black Body Radiation) The Spikes and Valleys (Specific Absorptions by Materials between the eye and the sun. Ask Students: As the temperature of the object changes, how will the shape of Figure 2.3 change? Group Activity 2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University Dr. Hunter’s Class Chemistry 500 Topic 2. 20 2F Wave/Particle Duality Light is Wave Like Evidence includes Diffraction I.e., light bends Light is Particle Like Evidence includes Photoelectric Effect I.e., there is a threshold energy for light to cause its effects Wave / Particle Duality Light has Both Wave and Particle Like Properties Plank’s Relationship E = h h is Plank’s Constant ( 6.63 x 10-34 joule seconds) Higher Frequency Higher Energy Lower Frequency Lower Energy Wave Packet Model 2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University Dr. Hunter’s Class Chemistry 500 Topic 2. 21 2G The Ozone Screen Graphics from Text: Figure 2.4 (3rd Edition only), Atmospheric Sunscreen The atmosphere (and especially the Stratospheric Ozone Layer) acts as sunscreen to select out which wavelengths of light reach the earth’s surface Graphics from Text: Figure 2.4 in 2nd Edition and 2.5 in 3rd Edition, Atmosphere’s effect on solar radiation reaching the earth’s surface The atmosphere “screens” us from high energy UV light reaching the surface Graphics from Text: Figure 2.5 in 2nd Edition and 2.6 in 3rd Edition, Ozone’s Absorption of Ultra-Violet Radiation Ozone absorbs high energy UV light 2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University Dr. Hunter’s Class Chemistry 500 Topic 2. 22 Molecular reasons for these effects Molecular Oxygen, O2, absorbs the highest energy UV light UV light with less than about 242 nm O2 + photon 2 O Ozone, O3, absorbs the medium energy UV light UV light with less than about 320 nm (i.e., lower energy) Ozone has a typical lifetime of about one or two hundred seconds Ozone has a weaker O-O bond than molecular oxygen and this bond is therefore broken by lower energy photons O3 + photon O2 + O 2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University Dr. Hunter’s Class Chemistry 500 Topic 2. 23 Ozone Cycle Ozone generation in the atmosphere O + O2 03 (formation of ozone) Graphics from Text: Figure 2.7 in 2nd Edition and 2.11 in 3rd Edition, Ozone concentration profile of the atmosphere Ozone concentrations are highest in the part of the stratosphere referred to as the Ozone Layer Graphics from Text: Figure 2.6 in 2nd Edition and 2.10 in 3rd Edition, The Chapman Cycle of Ozone in the Atmosphere 2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University Dr. Hunter’s Class Chemistry 500 Topic 2. 24 Ozone Destruction Free Radicals!!! Radicals are molecules or atoms with one or more unpaired electrons This makes them extremely reactive and they can catalyze reaction such as Ozone destruction H2O + energy H. + .OH H. + O3 .OH + O2 OH + O .H + O2 . H. + O3 + .OH + O .OH + O2 + .H + O2 Net Reaction: O + O3 2 O2 2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University Dr. Hunter’s Class Chemistry 500 Topic 2. 25 Ozone Loss Arctic and Antarctic Sensitivity Caused by extreme cold tiny crystals whose surfaces are involved in Ozone destruction Note: Noise levels in data Graphics from Text: Figure 2.8 in 2nd Edition and 2.7/2.12 in 3rd Edition, Average Ozone loss on the earth A few percent in continental US Graphics from Text: Figure 2.9 in 2nd Edition and 2.13 in 3rd Edition, Ozone loss in Antarctica About 50% in the high Antarctic 2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University Dr. Hunter’s Class Chemistry 500 Topic 2. 26 2H CFCs and Ozone Halocarbons Compounds containing only C, Cl, F, Br, and H Are typically expensive but safe non-toxic, non-flammable, non-reactive, and quite volatile Used as refrigerants, blowing agents, propellants, cleaning agents for computer parts, dry cleaning fluids, decaffination 2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University Dr. Hunter’s Class Chemistry 500 Topic 2. 27 Classes of Halocarbons CFCs are Chlorofluorocarbons These are chemicals that contain only C, Cl, and F Examples include: CFCl3 (Freon 11) and CF2Cl2 (Freon 12) Halons contain C, Br, and F and/or Cl Examples include: CH3Br, CF2Br2 and CClBr3 Used for fire extinguishers Chlorocarbons contain C, Cl, and H Examples include CCl3-CH3 and CH2Cl2 2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University Dr. Hunter’s Class Chemistry 500 Topic 2. 28 Halocarbons and Ozone Destruction They are generally safe at ground level, why are they dangerous in the Stratosphere? They are so stable that unlike most chemicals they escape destruction in the decade or so it takes them to make it to the Stratosphere This means that they can transfer Chlorine and Bromine atoms here much better than other chemicals In the Stratosphere, these Cl and Br containing compounds produce Cl. and Br. radicals which catalyze Ozone destruction Bromine radicals are much less concentrated but are much more destructive The man made examples of halocarbons are typically more stable than the natural ones and therefore typically make it to the Stratosphere better 2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University Dr. Hunter’s Class Chemistry 500 Topic 2. 29 Reactions that destroy Ozone CF2Cl2 + energy CF2Cl. + .Cl Cl. + O3 .OCl + O2 OCl + O Cl. + O2 . Cl. + O3 + . OCl + O . OCl + O2 + .Cl + O2 O + O3 2 O2 Net Reaction: Note: this reaction is very similar to that for Ozone destruction by hydrogen radicals, it is just much faster and thus more efficient The analogous reaction with bromine radicals is even faster and more efficient Graphics from Text: Figure 2.11 in 2nd Edition and 2.15 in 3rd Edition, Chlorine - Ozone Correlations 2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University Dr. Hunter’s Class Chemistry 500 Solutions? Many now in place or being put into effect “Montreal Treaty” Cost Concerns Safety Concerns Technology Concerns Hydrochlorofluorocarbons Supercritical CO2 Greenhouse gasses 2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University Topic 2. 30 Chemistry 500 Dr. Hunter’s Class Topic 2. 31 Index of Vocabulary and Major Topics 1 12 C ..............................................................................8 C ........................................................................ 8, 10 14 C ..............................................................................8 183 W ......................................................................... 10 19 F ............................................................................ 10 1 H ..............................................................................8 13 2 235 U ............................................................................8 U ............................................................................8 29 Si ........................................................................... 10 2 H ..............................................................................8 238 3 3 H ..............................................................................8 4 40 Ar ............................................................................9 4 He .............................................................................9 7 7 Be ........................................................................... 10 A Allotropes .............................................................. 4, 5 Amplitude .......................................................... 17, 18 Analytical Data ........................................................ 11 Antarctic .................................................................. 25 Arc Welding ..............................................................3 Arctic ....................................................................... 25 Ask Students ................................................ 10, 16, 19 atmosphere .................................................................8 Atmospheric Sunscreen ........................................... 21 Atomic Number .........................................................9 Atoms ........................................................................6 Average Ozone loss on the earth ............................. 25 B blowing agents ......................................................... 26 bond ......................................................................... 15 Bond Angles ............................................................ 15 Bond Lengths........................................................... 15 Bonds ....................................................................... 13 C catalyze .................................................................... 24 CCl3-CH3 ................................................................. 27 CClBr3 ..................................................................... 27 CF2Br2...................................................................... 27 CF2Cl2 ...................................................................... 27 CFC ......................................................................... 27 CFCl3 ....................................................................... 27 CFCs and Ozone ...................................................... 26 CH2Cl2 ..................................................................... 27 CH3Br ...................................................................... 27 Chapman Cycle ....................................................... 23 Charge .......................................................................7 Chlorine - Ozone Correlations ................................. 29 Chlorocarbons.......................................................... 27 Chlorofluorocarbon ................................................. 27 cleaning agents for computer parts .......................... 26 Core Electrons ...........................................................6 Cost Concerns .......................................................... 30 D D ..............................................................................8 decaffination ............................................................ 26 Deuterium ..................................................................8 Diamond ....................................................................4 Diatomic Molecule ....................................................5 Diffraction ............................................................... 20 dry cleaning fluids ................................................... 26 E e- .......................................................................... 7, 9 E = h ..................................................................... 20 Electrical Discharges .................................................3 electricity ................................................................. 13 Electromagnetic Spectrum ................................. 17, 19 Electromagnetic Waves ........................................... 17 Electron Cloud ...........................................................6 Electrons ................................................................ 7, 9 Electrostatic Force .....................................................7 element .................................................................. 4, 8 Energy .......................................................................3 expensive but safe .................................................. See experimental data ..................................................... 13 F Free Radicals ........................................................... 24 Freon ........................................................................ 27 Frequency .................................................... 17, 18, 20 C ............................................................................ 17 Carbon .......................................................................4 2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University Chemistry 500 Dr. Hunter’s Class G Graphics from Text ................ 6, 17, 19, 21, 23, 25, 29 Graphite .....................................................................4 Greenhouse gasses ................................................... 30 Group Activity ............................................. 10, 16, 19 H Halocarbons ....................................................... 26, 27 Halocarbons and Ozone Destruction ....................... 28 Halons ...................................................................... 27 How Do We Explain Molecular Structures ............. 13 How Do We Know Molecular Structures ................ 11 Hydrochlorofluorocarbons ....................................... 30 Hydrogen ...................................................................8 I in Stable Nuclei .........................................................7 Infra-Red.................................................................. 11 intensity ................................................................... 18 IR ............................................................................ 11 isotope .......................................................................9 Isotopes ......................................................................8 L Laser Printers .............................................................3 Lewis ....................................................................... 13 Lewis Dot Structures ............................................... 13 lifetime ..................................................................... 22 Light has Both Wave and Particle Like Properties .. 20 Light is Particle Like ............................................... 20 Light is Wave Like .................................................. 20 Lightning ...................................................................3 Liquefies ....................................................................5 lone pairs ................................................................. 15 Lone Pairs ................................................................ 13 M Magnetic Resonance Imaging.................................. 11 Mass....................................................................... 7, 8 Mass Number .............................................................9 Molecular Oxygen ....................................... 3, 4, 5, 22 molecular shapes...................................................... 11 molecular structures ................................................. 11 Montreal Treaty ....................................................... 30 MRI ......................................................................... 11 N n .......................................................................... 7, 9 Net Reaction ............................................................ 24 neutral atom ...............................................................9 Neutron ......................................................................7 Neutron/Proton Ratio .................................................7 Neutrons ....................................................................9 NMR .................................................................... 8, 11 Noise levels in data .................................................. 25 Topic 2. 32 non-flammable ......................................................... 26 non-reactive ............................................................. 26 non-toxic .................................................................. 26 Nuclear Magnetic Resonance .................................. 11 Nuclei ........................................................................6 Nucleus .................................................................. 6, 7 O O2 .................................................................... 3, 5, 22 O3 .................................................................... 3, 5, 22 Octet ........................................................................ 14 Odorless .....................................................................5 Organic Compounds ................................................ 15 Oxygen ......................................................................4 Ozone..................................................... 3, 4, 5, 21, 22 Ozone concentration profile of the atmosphere ....... 23 Ozone Cycle ............................................................ 23 Ozone Destruction ................................................... 24 Ozone generation ..................................................... 23 Ozone Loss .............................................................. 25 Ozone loss in Antarctica .......................................... 25 P P+ .......................................................................... 7, 9 pencil lead ..................................................................4 periodic table ........................................................... 13 Periodic Table ............................................................9 Photochemical Smog .................................................3 Photoelectric Effect ................................................. 20 photon ...................................................................... 22 Plank’s Constant ...................................................... 20 Plank’s Relationship ................................................ 20 propellants ............................................................... 26 properties ...................................................................4 Protons ................................................................... 7, 9 pulp and paper bleaching ...........................................5 Q Quick and Dirty Method for getting Lewis Structures ............................................................................ 15 R Radicals ................................................................... 24 radioactive .................................................................8 radioactivity ............................................................. 13 Reactions that destroy Ozone .................................. 29 refrigerants ............................................................... 26 Rigorous Method of Determining Lewis Dot Structures ............................................................ 14 Rubber Baggie model of nucleus ...............................8 S Safety Concerns ....................................................... 30 shared pairs of electrons .......................................... 13 Single Crystals ......................................................... 12 Spectroscopic Methods ............................................ 11 2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University Chemistry 500 Dr. Hunter’s Class Speed of Light ......................................................... 17 Sporting Methods .................................................... 11 Stratosphere ............................................................. 28 Stratospheric Ozone Layer ...................................... 21 Strong Nuclear Force .................................................7 structures....................................................................4 Sub-Atomic Particles .................................................6 Supercritical CO2 ..................................................... 30 T T ..............................................................................8 Technology Concerns .............................................. 30 Tesla Coils .................................................................3 The Ozone Screen .................................................... 21 Theory ..................................................................... 13 threshold energy ...................................................... 20 Triatomic Molecule ...................................................5 Tritium .......................................................................8 U Ultra Violet-Visible ................................................. 11 Ultra-Violet Radiation ............................................. 21 unpaired electrons .................................................... 24 UV light ............................................................. 21, 22 UV-Vis .................................................................... 11 Topic 2. 33 V Valence Electrons ................................................ 6, 13 volatile ..................................................................... 26 W water purification .......................................................5 Wave / Particle Duality............................................ 20 Wave Motion ........................................................... 17 Wave Packet Model ................................................. 20 Wave/Particle Duality.............................................. 20 Wavelength .............................................................. 17 Waves of Light ........................................................ 17 What is Ozone ...........................................................3 What is the Structure of a Atom ................................6 X X-Ray Crystallography/Diffraction ......................... 12 ................................................................ 17, 18, 22 ...................................................................... 17, 18 2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University